WO2022139187A1 - Matériau actif d'électrode positive pour batterie secondaire au lithium et procédé de production de celui-ci, et batterie secondaire au lithium - Google Patents

Matériau actif d'électrode positive pour batterie secondaire au lithium et procédé de production de celui-ci, et batterie secondaire au lithium Download PDF

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WO2022139187A1
WO2022139187A1 PCT/KR2021/016919 KR2021016919W WO2022139187A1 WO 2022139187 A1 WO2022139187 A1 WO 2022139187A1 KR 2021016919 W KR2021016919 W KR 2021016919W WO 2022139187 A1 WO2022139187 A1 WO 2022139187A1
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active material
lithium
secondary battery
lithium secondary
positive electrode
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PCT/KR2021/016919
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English (en)
Korean (ko)
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박인철
김형섭
이상혁
송정훈
김정훈
남상철
최권영
권오민
송석현
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주식회사 포스코
재단법인 포항산업과학연구원
(주)포스코케미칼
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Priority to CN202180087073.7A priority Critical patent/CN116670854A/zh
Priority to EP21911254.7A priority patent/EP4266421A1/fr
Priority to JP2023538659A priority patent/JP2024500473A/ja
Publication of WO2022139187A1 publication Critical patent/WO2022139187A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • LiMO 2 , M Ni, Co, Mn, etc.
  • LiNiO 2 and high nickel layered positive electrode materials have the highest capacity.
  • Ni(III) it is difficult to synthesize a stoichiometric material, and there is a small change in lithium in the synthesis process.
  • electrochemical properties change significantly.
  • a lithium-excess high nickel-based positive electrode active material having high price competitiveness, high stability, and high energy density, a method for manufacturing the same, and a lithium secondary battery including the same.
  • the molar content of lithium present in the structure of the positive electrode active material, measured through neutron diffraction analysis, is 1.01 to 1.15 lithium with respect to 1 mole of the positive electrode active material
  • a positive active material for a secondary battery is provided.
  • M 1 is at least one selected from Co, Mn, Al, Mg, Ca, Ti, V, Cr, Zr, Nb, Mo, and W is an element
  • a precursor containing the compound represented by Formula 2 and a lithium raw material are mixed in a molar ratio of 1: 1.03 to 1: 1.3, and heat-treated in a temperature range of 680 ° C to 780 ° C.
  • a method for manufacturing a positive electrode active material is provided.
  • M 11 is at least one element selected from Co, Mn, Al, Mg, Ca, Ti, V, Cr, Zr, Nb, Mo, and W.
  • a lithium secondary battery including a positive electrode, a negative electrode, a separator and an electrolyte including the positive electrode active material is provided.
  • a cathode active material according to an embodiment and a lithium secondary battery including the same realize high price competitiveness, high stability, high energy density, high capacity, and high lifespan characteristics.
  • FIG. 1 is a schematic diagram showing the chemical structure of a lithium-excess high nickel-based positive electrode active material.
  • FIG. 11 is a graph analyzing the lithium content in the structures of the positive electrode active materials of Examples 1 to 12 and Comparative Examples 1 to 6;
  • 15 is a graph showing the electrochemical characteristics of the batteries of Examples 1, 2, 4 and 6.
  • 17 is a graph showing the lifespan characteristics of the batteries of Examples 7, 8, 10 and 12.
  • the term “layer” herein includes not only a shape formed on the entire surface when viewed from a plan view, but also a shape formed on a partial surface.
  • the average particle diameter may be measured by a method well known to those skilled in the art, for example, may be measured by a particle size analyzer, or may be measured by a transmission electron micrograph or a scanning electron micrograph. Alternatively, it is possible to obtain an average particle size value by measuring using a dynamic light scattering method, performing data analysis, counting the number of particles for each particle size range, and calculating from this. Unless otherwise defined, the average particle diameter may mean the diameter (D50) of particles having a cumulative volume of 50% by volume in the particle size distribution.
  • the positive active material for a lithium secondary battery is a lithium-excess high nickel-based layered positive electrode active material including a compound represented by Formula 1 below.
  • M 1 is at least one selected from Co, Mn, Al, Mg, Ca, Ti, V, Cr, Zr, Nb, Mo, and W is an element
  • the lithium excess means that the lithium occupies a part of the transition metal sites due to the excess lithium entering the structure of the active material.
  • 1 is a diagram showing the chemical structure of a positive electrode active material according to an embodiment, and shows a structure in which excess lithium is contained in a portion of a transition metal site such as Ni, Co, and/or Mn.
  • the molar content of lithium present in the structure of the positive active material is 1.01 to 1.15 with respect to 1 mole of the positive active material.
  • the molar content of lithium may be measured, for example, through neutron diffraction analysis.
  • the molar content of lithium present in the structure of the cathode active material may be expressed as 1.01 to 1.15 per mole of the compound represented by Formula 1 above.
  • the range of a in (1+a) representing the lithium content in the structure of the active material may be, for example, 0.005 ⁇ a ⁇ 0.19, 0.01 ⁇ a ⁇ 0.17, or 0.01 ⁇ a ⁇ 0.15.
  • the high nickel-base means that the content of nickel in the active material is high, and specifically, it may mean that the content of nickel is more than 80 mol% based on the total content of metals excluding lithium, for example, the content of nickel may be 81 mole % or greater, 85 mole % or greater, 89 mole % or greater, 90 mole % or greater, or 90 mole % or greater.
  • the b value representing the nickel content in Formula 1 is, for example, 0.81 ⁇ b ⁇ 0.99, 0.83 ⁇ b ⁇ 0.99, 0.85 ⁇ b ⁇ 0.99, 0.87 ⁇ b ⁇ 0.99, 0.89 ⁇ b ⁇ 0.99, 0.90 ⁇ b ⁇ 0.99 , 0.91 ⁇ b ⁇ 0.99, 0.92 ⁇ b ⁇ 0.99, or 0.81 ⁇ b ⁇ 0.98.
  • the positive electrode active material according to the exemplary embodiment is a high nickel-based material having a nickel content exceeding 80 mol%, and a lithium-excessive positive electrode active material having a lithium content of 1.01 to 1.15 mol content into the active material structure.
  • the high nickel-based positive electrode active material realizes a high capacity, but first of all, the synthesis itself is difficult and structural stability is difficult to secure. This problem frequently occurs and it is difficult to secure battery safety.
  • lithium raw material is added during synthesis to lower cation mixing and increase capacity, lithium does not enter the active material structure and remains in the form of impurities such as Li 2 CO 3 or Li 2 O in many cases, and these impurities are reduce the dose and cause stability problems.
  • the present inventors have found that the electrochemical properties of the lithium-excess high nickel-based layered positive electrode active material are greatly changed due to a slight change in the lithium composition and a change in the synthesis temperature, and the synthesis is performed in a specific temperature range within a specific lithium content range.
  • a stable positive electrode active material with a very high nickel content and a certain amount of lithium entered into the active material structure could be successfully synthesized.
  • the battery life characteristics and stability were improved while the synthesized positive active material realized high capacity and high energy density.
  • the cation mixing which means the content of nickel in the lithium site, is less than 5 atomic %.
  • the capacity is reduced due to excessive cation mixing in which Ni 2+ ions occupy lithium sites.
  • excess lithium occupies some of the transition metal sites, and the average oxidation number of the transition metal increases, and thus the cation mixing is decreased.
  • the average oxidation number of nickel was increased due to excess lithium, the formation of a rock salt phase of the Ni(II)-O bond on the surface of the positive electrode active material was suppressed, and the cation mixing was reduced, thereby suppressing the elution of nickel.
  • the cation mixture may be, for example, less than 4.5 atomic %, less than 4.0 atomic %, or less than 3.5 atomic %. When the cation mixing satisfies the above range, the positive active material may realize sufficient capacity and secure battery stability.
  • the positive active material has a very low content of impurities such as Li 2 CO -3 and Li 2 O remaining in the active material because excessively added lithium has been successfully introduced into the active material structure.
  • the content of Li 2 CO- 3 present in the positive active material may be less than 0.5 wt%, for example, less than 0.4 wt%.
  • the content of Li 2 O present in the positive active material may be less than 1.0 wt%, for example, less than 0.8 wt% or less than 0.5 wt%.
  • the content of Li 2 CO -3 and Li 2 O may be measured, for example, through X-ray diffraction analysis.
  • Chemical Formula 1 may be specifically represented by Chemical Formula 2 below.
  • M 2 is Co, Al, Mg, Ca, Ti, V, Cr, It is at least one element selected from Zr, Nb, Mo, and W.
  • the positive active material including the compound represented by Formula 2 may exhibit excellent battery characteristics such as high lifespan characteristics while implementing high capacity.
  • Chemical Formula 1 may be specifically represented by Chemical Formula 3 below.
  • M 3 is Mn, Al, Mg, Ca, Ti, V, Cr, It is at least one element selected from Zr, Nb, Mo, and W.
  • the positive active material including the compound represented by Formula 3 may exhibit excellent battery characteristics such as high lifespan characteristics while implementing high capacity.
  • Chemical Formula 1 may be specifically represented by Chemical Formula 4 below.
  • M 4 is Al, Mg, Ca, It is at least one element selected from Ti, V, Cr, Zr, Nb, Mo, and W.
  • the positive electrode active material including the compound represented by Formula 4 may exhibit excellent battery characteristics such as high lifespan characteristics while realizing a high capacity.
  • the average particle diameter of the positive active material may be about 2 ⁇ m to 25 ⁇ m, for example, 5 ⁇ m to 25 ⁇ m, 10 ⁇ m to 25 ⁇ m, or 10 ⁇ m to 20 ⁇ m.
  • a positive electrode active material having a high tap density and a high energy density per volume may be implemented.
  • the average particle diameter may be analyzed by, for example, an optical microscope such as a scanning electron microscope, and may mean the diameter (D50) of particles having an accumulated volume of 50% by volume in the particle size distribution.
  • the method for producing the positive active material includes mixing a positive electrode active material precursor containing a compound represented by the following Chemical Formula 11 and a lithium raw material in a molar ratio of 1: 1.03 to 1: 1.3 and heat-treating at a temperature of 650 ° C. to 780 ° C. do.
  • M 11 is at least one element selected from Co, Mn, Al, Mg, Ca, Ti, V, Cr, Zr, Nb, Mo, and W.
  • this manufacturing method it is possible to successfully synthesize a layered positive electrode active material having a high nickel-based material having a nickel content of more than 80 mol% and having an excess lithium into the structure, and the synthesized positive electrode active material has high capacity and high energy density. It is possible to exhibit excellent battery characteristics such as high lifespan characteristics while implementing.
  • the compound represented by Chemical Formula 11 is a metal hydroxide containing nickel, and is a precursor of the positive electrode active material.
  • b11 represents the molar content of nickel with respect to the total metal content, and for example, 0.81 ⁇ b11 ⁇ 0.99, 0.83 ⁇ b11 ⁇ 0.99, 0.85 ⁇ b11 ⁇ 0.99, 0.87 ⁇ b11 ⁇ 0.99, 0.89 ⁇ b11 ⁇ 0.99, 0.90 ⁇ b11 ⁇ 0.99, 0.91 ⁇ b11 ⁇ 0.99, 0.92 ⁇ b11 ⁇ 0.99, or 0.81 ⁇ b11 ⁇ 0.98.
  • the success or failure of the synthesis is divided even with a slight change in the amount of lithium added, and the electrochemical properties of the synthesized active material are greatly changed.
  • the high nickel-based metal hydroxide precursor and the lithium raw material are mixed in a molar ratio of 1: 1.03 to 1: 1.3 and heat-treated in a temperature range of 680 ° C to 780 ° C. Excess lithium to realize high capacity while maintaining a stable structure A high nickel-based positive electrode active material was successfully synthesized.
  • the mixing ratio of the metal hydroxide precursor and the lithium raw material may be, for example, a molar ratio of 1: 1.03 to 1: 1.25, or 1: 1.03 to 1: 1.2.
  • the heat treatment temperature may be, for example, 680 °C to 750 °C, 680 °C to 730 °C, 680 °C to 710 °C, 680 °C to 700 °C, or 690 °C to 780 °C, or 700 °C to 750 °C.
  • the desired lithium-excess high nickel-based positive electrode active material may be successfully synthesized. That is, as a material in which the content of nickel exceeds 80 mol%, it is possible to successfully synthesize a lithium-excess positive electrode active material in which the molar content of lithium present in the structure satisfies 1.01 to 1.15.
  • the synthesized positive active material may exhibit excellent battery characteristics such as high lifespan characteristics while implementing high capacity and high energy density.
  • the metal hydroxide that is, the precursor of the positive electrode active material may be prepared by a general co-precipitation method.
  • the precursor is an aqueous solution of a metal salt containing a nickel raw material such as a nickel salt, and an aqueous alkali solution such as an aqueous ammonia solution as a chelating agent, etc. 2 can be prepared by co-precipitation reaction while injecting.
  • the nickel salt may be nickel sulfate, nickel nitrate, nickel chloride, nickel fluoride, or a combination thereof.
  • the aqueous metal salt solution may further include a cobalt salt, a manganese salt, an aluminum salt, etc. in addition to the nickel salt.
  • the cobalt salt may be, for example, cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt fluoride, or a combination thereof.
  • the manganese salt may be, for example, manganese sulfate, manganese nitrate, manganese chloride, manganese fluoride, or a combination thereof
  • the aluminum salt is, for example, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum fluoride, or a combination thereof.
  • the lithium raw material may include, for example, Li 2 CO 3 , LiOH, or a combination thereof.
  • a positive electrode comprising the above-described positive active material; cathode; separator; and a lithium secondary battery including a non-aqueous electrolyte.
  • the positive electrode includes a current collector and a positive electrode active material layer disposed on the current collector.
  • the positive active material layer may include a positive active material, and the positive active material may include the positive active material for a lithium secondary battery according to the exemplary embodiment described above.
  • the content of the cathode active material may be 90 wt% to 99 wt% based on the total weight of the cathode active material layer.
  • the positive active material layer may further include a binder and/or a conductive material.
  • the content of the binder and the conductive material may be 1 wt% to 5 wt%, respectively, based on the total weight of the positive electrode active material layer.
  • the binder serves to well adhere the positive active material particles to each other and also to adhere the positive active material to the current collector.
  • Representative examples of the binder include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, a polymer including ethylene oxide, polyvinyl pyrrol Don, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, etc. may be used, but the present invention is not limited thereto. .
  • the conductive material is used to impart conductivity to the electrode, and in the configured battery, any electronically conductive material may be used without causing a chemical change.
  • the conductive material include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, and carbon fiber; Metal-based substances, such as metal powders, such as copper, nickel, aluminum, and silver, or a metal fiber; conductive polymers such as polyphenylene derivatives; or a conductive material containing a mixture thereof.
  • the positive electrode current collector may be an aluminum foil, a nickel foil, or a combination thereof, but is not limited thereto.
  • the negative electrode includes a current collector and a negative active material layer formed on the current collector, and the negative active material layer includes a negative electrode active material.
  • the negative active material includes a material capable of reversibly intercalating/deintercalating lithium ions, lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, or a transition metal oxide.
  • the material capable of reversibly intercalating/deintercalating the lithium ions is a carbon material, and any carbon-based negative active material generally used in lithium ion secondary batteries may be used, and a representative example thereof is crystalline carbon. , amorphous carbon or these may be used together.
  • the lithium metal alloy includes lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al and Sn from the group consisting of Alloys of metals of choice may be used.
  • Materials capable of doping and dedoping lithium include Si, SiO x (0 ⁇ x ⁇ 2), Si-Y alloy (where Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, An element selected from the group consisting of rare earth elements and combinations thereof, but not Si), Sn, SnO 2 , Sn-Y (wherein Y is an alkali metal, an alkaline earth metal, a group 13 element, a group 14 element, a transition metal, a rare earth) It is an element selected from the group consisting of elements and combinations thereof, and is not Sn) and the like.
  • the negative active material layer also includes a binder, and may optionally further include a conductive material.
  • the binder serves to well adhere the negative active material particles to each other and also to adhere the negative active material to the current collector.
  • the conductive material is used to impart conductivity to the electrode, and in the configured battery, any electronically conductive material may be used without causing a chemical change.
  • the current collector one selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with conductive metal, and combinations thereof may be used.
  • the negative electrode and the positive electrode are prepared by mixing an active material, a conductive material, and a binder in a solvent to prepare an active material composition, and applying the composition to a current collector. Since such an electrode manufacturing method is widely known in the art, a detailed description thereof will be omitted herein.
  • the solvent may include, but is not limited to, N-methylpyrrolidone.
  • the electrolyte includes a non-aqueous organic solvent and a lithium salt.
  • the non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • the lithium salt is dissolved in an organic solvent, acts as a source of lithium ions in the battery, enables basic lithium secondary battery operation, and serves to promote movement of lithium ions between the positive electrode and the negative electrode.
  • a separator may exist between the positive electrode and the negative electrode.
  • a separator polyethylene, polypropylene, polyvinylidene fluoride, or a multilayer film of two or more layers thereof may be used.
  • a polyethylene/polypropylene two-layer separator, a polyethylene/polypropylene/polyethylene three-layer separator, and polypropylene/polyethylene/poly It goes without saying that a mixed multilayer film such as a propylene three-layer separator or the like can be used.
  • Lithium secondary batteries can be classified into lithium ion batteries, lithium ion polymer batteries, and lithium polymer batteries depending on the type of separator and electrolyte used, and can be classified into cylindrical, prismatic, coin-type, pouch-type, etc. according to the shape, According to the size, it can be divided into a bulk type and a thin film type. Since the structure and manufacturing method of these batteries are well known in the art, a detailed description thereof will be omitted.
  • a cathode active material precursor having a composition of Ni 0.92 Co 0.04 Mn 0.04 (OH) 2 is prepared by a general co-precipitation method. Specifically, an aqueous metal salt solution is prepared by dissolving NiSO 4 ⁇ 6H 2 O, CoSO 4 ⁇ 7H 2 O, and MnSO 4 ⁇ H 2 O in distilled water. After preparing the co-precipitation reactor, N 2 is injected to prevent oxidation of metal ions during the co-precipitation reaction, and the reactor temperature is maintained at 50°C. NH 4 (OH) as a chelating agent is added to the coprecipitation reactor, and NaOH is added to adjust pH. The precipitate obtained according to the co-precipitation process is filtered, washed with distilled water, and dried in an oven at 100° C. for 24 hours to prepare a cathode active material precursor having an average diameter of about 14.8 ⁇ m.
  • the prepared cathode active material precursor and LiOH ⁇ H 2 O were mixed in a molar ratio of 1:1.03, put into a tube furnace, and fired while introducing oxygen at 50 mL/min. After raising the temperature to 700 DEG C at a rate of 10 DEG C/min, this temperature is maintained for 12 hours, and then the product is naturally cooled to 25 DEG C.
  • the precursor of the positive active material, the positive active material, and the battery were prepared in the same manner except that the mixing ratio of the positive active material precursor and LiOH H 2 O and the heat treatment temperature were changed as shown in Table 1 below. manufacture
  • Example 1 Molar ratio of lithium raw material to precursor Firing temperature (°C) Example 1 1.03 700 Example 2 1.06 700 Example 3 1.10 700 Example 4 1.16 700 Example 5 1.20 700 Example 6 1.30 700 Example 7 1.03 750 Example 8 1.06 750 Example 9 1.10 750 Example 10 1.16 750 Example 11 1.20 750 Example 12 1.30 750 Comparative Example 1 1.03 800 Comparative Example 2 1.06 800 Comparative Example 3 1.10 800 Comparative Example 4 1.16 800 Comparative Example 5 1.20 800 Comparative Example 6 1.30 800
  • FIGS. 2 to 4 X-ray diffraction analysis was performed on the positive active materials prepared in Examples 1 to 12 and Comparative Examples 1 to 6, and the results are shown in FIGS. 2 to 4 .
  • 2 is an X-ray diffraction pattern of the active materials of Comparative Examples 1 to 6
  • FIG. 3 is an X-ray diffraction pattern of the active materials of Examples 7 to 12
  • FIG. 4 is an X-ray diffraction pattern of the active materials of Examples 1 to 6.
  • FIGS. 1 X-ray diffraction patterns of FIGS.
  • the contents of residual impurities Li 2 CO 3 , and Li 2 O were measured through Rietveld analysis using X-ray diffraction analysis for the positive active materials prepared in Examples 1 to 12 and Comparative Examples 1 to 6, and Comparative Example 1
  • the content of impurities in the positive active material of Examples 7 to 12 is shown in FIG. 6, and the content of impurities in the positive active material of Examples 1 to 6 is shown in FIG. 7 shows. 5 , it can be seen that, in Comparative Examples 1 to 6, excess lithium does not enter the active material structure and remains in the form of impurities Li 2 CO 3 , Li 2 O, and the like.
  • the impurity content was greatly reduced, and in the case of Examples 1 to 6 in FIG. 7 , it could be confirmed that the impurities were hardly present, so that excess lithium penetrated into the active material structure.
  • the oxidation number of nickel was analyzed through X-ray absorption near-edge structure (XANES) analysis of the positive active materials prepared in Examples 1 to 12 and Comparative Examples 1 to 6, and Comparative Examples 1 to 6
  • XANES X-ray absorption near-edge structure
  • FIG. 8 The change in the oxidation number of nickel in the positive active material of 6 is shown in FIG. 8, the change in the oxidation number of nickel in the positive active material of Examples 7 to 12 is shown in FIG. 9, and the change in the oxidation number of nickel in the positive active material of Examples 1 to 6 is shown in FIG. 10 .
  • lithium penetrates into the structure of the active material to form an excess structure of lithium lithium occupies the site of the transition metal, and the oxidation number of the remaining transition metal increases.
  • Evaluation Example 4 Analysis of lithium content in the structure of the cathode active material through neutron diffraction analysis
  • the half cells prepared in Examples 1 to 12 and Comparative Examples 1 to 6 were charged with cut-off at 4.9 V, and the electrochemical characteristics of the batteries of Comparative Examples 1, 2, 4 and 6 are shown in FIG. 13 .
  • the electrochemical properties of the batteries of Examples 7, 8, 10 and 12 are shown in FIG. 14, and the electrochemical properties of the batteries of Examples 1, 2, 4 and 6 are shown in FIG. 15.
  • a lithium-excess material that is, an active material containing excess lithium in the structure of the active material, exhibits an oxidation/reduction reaction of oxygen at a high voltage.
  • the batteries of Examples 1 to 12 shown in FIGS. 14 and 15 it can be seen that an irreversible reaction occurred in the 4.6 V subgroup during the first charge, and this reaction is generally known as an oxidation/reduction reaction of oxygen. Therefore, in Examples 1 to 12, it can be confirmed once again that the desired lithium-excess positive electrode active material was smoothly synthesized.
  • the batteries prepared in Examples 1 to 12 and Comparative Examples 1 to 6 were charged and discharged up to about 50 cycles to evaluate their lifespan characteristics, and the lifespan characteristics of the batteries of Comparative Examples 1, 2, 4 and 6 are shown in FIG. 16 , and the lifespan characteristics of the batteries of Examples 7, 8, 9 and 12 are shown in FIG. 17, and the lifespan characteristics of the batteries of Examples 1, 2, 3 and 6 are shown in FIG. 18. 16 to 18 , it can be seen that the batteries of the embodiments have high capacity and high lifespan characteristics.

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Abstract

La présente invention concerne un matériau actif d'électrode positive comprenant un composé représenté par la formule 1, un procédé de fabrication de celui-ci, et une batterie secondaire au lithium comprenant celui-ci, la teneur molaire en lithium présent dans la structure du matériau actif d'électrode positive, mesurée par analyse de diffraction de neutrons, étant de 1,01 à 1,15 par rapport à 1 mole du matériau actif d'électrode positive. [Formule chimique 1] Li1+a(NibM1 1-b)1-aO2, dans la formule chimique 1, 0<a<0,2, 0,8<b<1, et M1 est au moins un élément sélectionné parmi Co, Mn, Al, Mg, Ca, Ti, V, Cr, Zr, Nb, Mo et W.
PCT/KR2021/016919 2020-12-21 2021-11-17 Matériau actif d'électrode positive pour batterie secondaire au lithium et procédé de production de celui-ci, et batterie secondaire au lithium WO2022139187A1 (fr)

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CN202180087073.7A CN116670854A (zh) 2020-12-21 2021-11-17 正极活性物质及其制备方法、包括该物质的锂二次电池
EP21911254.7A EP4266421A1 (fr) 2020-12-21 2021-11-17 Matériau actif d'électrode positive pour batterie secondaire au lithium et procédé de production de celui-ci, et batterie secondaire au lithium
JP2023538659A JP2024500473A (ja) 2020-12-21 2021-11-17 リチウム二次電池用正極活物質とその製造方法およびリチウム二次電池

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